Water absorbing or water soluble polymers, intermediate compounds, and methods thereof

ABSTRACT

Disclosed are graft copolymers, compositions including graft copolymers, intermediate materials, and related methods, where the graft copolymer includes a first polymer component including a 1,1-disubstituted-1-alkene compound (preferably a methylene malonate compound) and is grafted to a second component. The resulting graft copolymer may be hydrophilic or water soluble. The second component preferably is a hydrophilic component.

CLAIM OF PRIORITY

This application claims the benefit of priority to U.S. ProvisionalPatent Applications 62/452,543 filed on Jan. 31, 2017 by Sullivan et al.and 62/345,334 filed on Jun. 3, 2016 by Palsule et al., and to U.S.patent application Ser. No. 15/234,191 filed on Aug. 11, 2016 by Palsuleet al., Ser. No. 15/437,164 filed on Feb. 20, 2017, and Ser. No.15/472,379 filed on Mar. 29, 2017, the contents of which are eachincorporated herein by reference in its entirety.

FIELD

Disclosed are novel polymers and polymeric compositions comprising afirst component including a polymer formed from polymerizing one or moremonomers including a 1,1-diester-alkene attached to a second componentthat is a hydrophilic component. The hydrophilic component preferablyincludes a hydrophilic polymer or a hydrophilic functional group.Preferred polymers are water absorbing polymers or polymers thatdissolve in water. Also disclose are intermediate compounds, and relatedmethods. The grafted polymer may be used in a variety of applicationsincluding as a surfactant, an ionomer, an antifouling agent, forpetroleum recovery, for water treatment, as a flocculant, forhydrometallurgy, as a detergent, in a pharmaceutical process, or anycombination thereof.

BACKGROUND

There is a need for new water absorbing polymer and new water solublepolymers for a variety of applications.

There is also a need for new hydrophilic polymers that are cross-linkedso that they do not dissolve in water.

There is also a need for polymers capable of absorbing high levels ofwater.

SUMMARY

One aspect of the teaching herein is directed at a grafted polymercomprising: a first component including a polymer formed by polymerizingone or more monomers including a 1,1-disubstituted-1-alkene compound,attached to a second component that is a hydrophilic component, whereinthe hydrophilic component includes a cation or a water-soluble polymer.

This aspect of the invention may be further characterized by one or anycombination of the following features: the polymer of the firstcomponent has a first end and a second end and a backbone connecting thefirst and a second ends, the backbone including about 92 atomic percentor more carbon atoms; the hydrophilic component is a water-solublepolymer selected from the group consisting of a polyacrylamide, apolyvinyl alcohol, a polyacrylic acid, a polyalkoxide (e.g., apolyethylene glycol homopolymer or a polyethylene glycol copolymer), anwater soluble amine containing polymer (e.g., polyamines,polyethyleneimines, and polymers including quaternary ammoniumcompounds), a copolymer of vinyl methyl ether and maleic anhydride,polyvinylpyrrolidone, a copolymer thereof, or any combination thereof;the second component includes a quaternary ammonium compound; the secondcomponent includes a polyalkoxide (preferably ethylene glycolhomopolymer or copolymer); the polyalkoxide includes 65 weight percentor more ethylene oxide groups, based on the total weight of thepolyalkoxide; the grafted polymer has a network structure (e.g., thegrafted polymer is cross-linked, includes a multi-functional monomer, orthe second component is attached to two or more1,1-disubstituted-1-alkene compounds); the one or more monomers includesa multifunctional 1,1-disubstiuted-1-alkene monomer (e.g., amultifunctional macromer) having two or more polymerizable alkenegroups; about 20 atomic percent or more (preferably about 30 atomicpercent or more, more preferably about 38 atomic percent or more, andmost preferably about 46 atomic percent or more) of the monomers of thefirst component are directly attached to the second component; the firstcomponent is present in an amount of about 10 weight percent or more(preferably about 15 weight percent or more, more preferably about 20weight percent or more, and even more preferably about 30 weight percentor more), based on the total weight of the graft polymer; the secondcomponent is present in an amount of about 20 weight percent or more(preferably about 30 weight percent or more, and more preferably about40 weight percent or more), based on the total weight of the graftpolymer; the total amount of the first component and the secondcomponent is about 50 weight percent or more (preferably about 70 weightpercent or more, even more preferably about 90 weight percent or more,and most preferably about 97 weight percent or more), based on the totalweight of the graft polymer; about 10 atomic percent or more of themonomers of the first component are 1,1-diester-1-alkenes that are freeof direct attachment to the hydrophilic component; the grafted polymerconsists essentially of the first component consisting only of one ormore 1,1-diester-1-alkene compounds, and the second component consistingonly of the water-soluble polymer or the cation; the grafted polymer isassociated with an anion; the anion includes a sulfonate ion or asulfate ion; the 1,1-disubstituted-1-alkene compound includes one ormore 1,1-diester-1-alkenes; the grafted polymer includes a sufficientamount of the second component so that the grafted polymer is watersoluble; or the grafted polymer includes about 30 to about 95 weightpercent of the water-soluble polymer, based on the total weight of thegrafted polymer.

Preferably the 1,1-disubstituted-1-alkene compound is a compound havinga structure:

wherein R is a hydrocarbyl group which may contain one or moreheteroatoms and X is oxygen or a direct bond (e.g, a methyleneß-ketoester). More preferably, the 1,1-disubstituted-1-alkene compoundis a methylene malonate having a structure:

wherein R is separately in each occurrence alkyl, alkenyl, C₃-C₉cycloalkyl, heterocyclyl, alkyl heterocyclyl, aryl, aralkyl, alkaryl,heteroaryl, or alkheteroaryl, or polyoxyalkylene, or both of the R'sform a 5-7 membered cyclic or heterocyclic ring (preferably R isseparately in each occurrence C₁-C₁₅ alkyl, C₂-C₁₅ alkenyl, C₃-C₉cycloalkyl, C₂₋₂₀ heterocyclyl, C₃₋₂₀ alkheterocyclyl, C₆₋₁₈ aryl, C₇₋₂₅alkaryl, C₇₋₂₅ aralkyl, C₅₋₁₈ heteroaryl or C₆₋₂₅ alkyl heteroaryl, orpolyoxyalkylene, or both of the R groups form a 5-7 membered cyclic orheterocyclic ring).

Another aspect of the present teachings is directed at a polymericcomposition including one or more of the grafted polymers according tothe teachings herein. Preferably the polymeric composition includesabout 10 weight percent or more of the grafted polymer, based on thetotal weight of the polymeric composition. Preferably, the polymericcomposition includes; about 0.5 to about 90 weight percent of one ormore compounds selected from the group consisting of a filler, astabilizer, a process aid, a biocide, a polymer, a colorant, a salt, andany combination thereof.

Another aspect of the present teachings is a polymerizable compositionincluding a 1,1-disubstituted-1-alkene compound grafted to awater-soluble polymer or to a compound including a cation (e.g., forpolymerizing the grafted polymer according to the teachings herein). Thewater-soluble polymer may be grafted to one, two or more1,1-disubstituted-1-alkene compounds. The grafted1,1-disubstituted-1-alkene compound may be grafted to one or twowater-soluble polymers (e.g., at opposing ends of the1,1-disubstituted-1-alkene compound). The 1,1-disubstituted-1-alkenecompound may be grafted to one or two cations (e.g., at opposing ends ofthe 1,1-disubstituted-1-alkene compound). The polymerizable compositionpreferably includes about 20 weight percent or more of grafted1,1-disubstituted-1-alkene compounds. The polymerizable composition mayoptionally include one or more 1,1-disubstituted-1-alkene compounds thatare free of graft (e.g., free of cation and free of water-solublepolymer). The polymerizable composition and/or the graft polymer mayinclude one or more cross-linkers. For example, the polymerizablecomposition may optionally include a multi-functional1,1-disubstituted-1-alkene compound having two or more polymerizablealkene groups. The polymerizable composition may include a catalyst foraccelerating a polymerization reaction of the 1,1-disubstituted-1-alkenecompound (e.g., the grafted 1,1-diester-alkene compound).

Another aspect according to the teachings herein is a method of forminga grafted compound comprising a step of grafting a 1,1-diester-1-alkenecompound with a quaternary ammonium compound or with a water-solublepolymer.

These aspects may be characterized by one or any combination of thefollowing features; the 1,1-diester-1-alkene is grafted on each of theesters; the grafting step is catalyzed by an acid catalyst (preferably abronsted acid) or an enzymatic catalyst; the grafting step includes atransesterification reaction; or the method includes a step ofpolymerizing the 1,1-diester-1-alkene compounds (preferably after thestep of grafting).

Preferably, the water-soluble polymer is selected from the groupconsisting of a polyacrylamide, a polyvinyl alcohol, a polyacrylic acid,a polyalkoxide (e.g., a polyethylene glycol homopolymer or apolyethylene glycol copolymer), an water soluble amine containingpolymer (e.g., polyamines, polyethyleneimines, and polymers includingquaternary ammonium compounds), a copolymer of vinyl methyl ether andmaleic anhydride, polyvinylpyrrolidone, a copolymer thereof, or anycombination thereof.

Another aspect of the teachings herein is a method of forming a graftedpolymer including a step of polymerizing a polymerizable composition,such as a polymerizable composition taught herein. The polymerizationreaction may be catalyzed by a surface or by a catalyst. A particularlypreferred catalyst is tetramethylguanidine.

Another aspect of the teachings herein is a conductive polymericcomposition comprising: a grafted polymer (e.g., a grafted polymer asdescribed herein) doped with one or more salts (e.g., at a concentrationof about 20 weight percent or more, based on the total weight of thecomposition).

Another aspect of the teachings herein is a coating comprising a graftedpolymer as described herein.

For various applications, the grafted polymer preferably is cross-linkedor has a network structure.

In various aspects, the grafted polymer maybe water soluble and/or thegrafted polymer may include a phase or component that is generally watersoluble. For example, the polymer may include a water solublepolyalkoxide. To prevent the polymer from dissolving when exposed towater, the grafted polymer may have a sufficient amount of cross-linking(e.g, by employing a sufficient amount of a cross-linker) so that anetwork structure is formed. The amount of cross-linking preferably issufficient so that the absorption of water by the polymer is constrainedby the stretching of the polymer segments between crosslink sites.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1A is an illustrative full scale H-NMR of transesterification ofDEMM with polyethylene glycol PEG 300. Formation of new species can beconfirmed in the 6.5 ppm methylene (double bond) region.

FIG. 1B is an illustrative H-NMR spectrogram of DEMM grafted withpolyethylene glycol PEG 300 polyol and including unreacted DEMM showingtwo species in the 6.5 ppm region of the spectrum in 1A. The amount ofthe transesterified species is around 35 percent and the amount ofunreacted DEMM is about 65 percent.

FIG. 2A is an illustrative H-NMR spectrogram of transesterification ofDEMM with glycerol ethoxylate. Formation of new species can be confirmedin the 6.5 ppm methylene (double bond) region.

FIG. 2B is an illustrative H-NMR spectrogram showing the integration ofthe two species seen in the 6.5 ppm region of the spectrum in FIG. 2A.The amount of transesterified species is around 42% and the amount ofunreacted DEMM is about 58 percent.

DETAILED DESCRIPTION

The explanations and illustrations presented herein are intended toacquaint others skilled in the art with the invention, its principles,and its practical application. Those skilled in the art may adapt andapply the invention in its numerous forms, as may be best suited to therequirements of a particular use. Accordingly, the specific embodimentsof the present invention as set forth are not intended as beingexhaustive or limiting of the teachings. The scope of the teachingsshould, therefore, be determined not with reference to the abovedescription, but should instead be determined with reference to theappended claims, along with the full scope of equivalents to which suchclaims are entitled. The disclosures of all articles and references,including patent applications and publications, are incorporated byreference for all purposes. Other combinations are also possible as willbe gleaned from the following claims, which are also hereby incorporatedby reference into this written description.

Unless defined otherwise, all technical and scientific terms used hereinhave the meaning commonly understood by a person skilled in the art towhich this disclosure belongs. The following references provide one ofskill with a general definition of many of the terms used in thisdisclosure: Singleton et al., Dictionary of Microbiology and MolecularBiology (2nd ed. 1994); The Cambridge Dictionary of Science andTechnology (Walker ed., 1988); The Glossary of Genetics, 5th Ed., R.Rieger et al. (eds.), Springer Verlag (1991); and Hale & Marham, TheHarper Collins Dictionary of Biology (1991).

Acid catalyst, as used herein, is an acidic species that catalyzes thetransesterification reaction while minimizing or not contributing toside reactions. One or more as used herein means that at least one, ormore than one, of the recited components may be used as disclosed.Nominal as used with respect to functionality refers to the theoreticalfunctionality; generally, this can be calculated from the stoichiometryof the ingredients used. Heteroatom refer to atoms that are not carbonor hydrogen such as nitrogen, oxygen, sulfur, and phosphorus;heteroatoms may include nitrogen and oxygen. Hydrocarbyl, as usedherein, refers to a group containing one or more carbon atom backbonesand hydrogen atoms, which may optionally contain one or moreheteroatoms. Where the hydrocarbyl group contains heteroatoms, theheteroatoms may form one or more functional groups well-known to oneskilled in the art. Hydrocarbyl groups may contain cycloaliphatic,aliphatic, aromatic, or any combination of such segments. The aliphaticsegments can be straight or branched. The aliphatic and cycloaliphaticsegments may include one or more double and/or triple bonds. Included inhydrocarbyl groups are alkyl, alkenyl, alkynyl, aryl, cycloalkyl,cycloalkenyl, alkaryl, and aralkyl groups. Cycloaliphatic groups maycontain both cyclic portions and noncyclic portions. Hydrocarbylenemeans a hydrocarbyl group or any of the described subsets having morethan one valence, such as alkylene, alkenylene, alkynylene, arylene,cycloalkylene, cycloalkenylene, alkarylene and aralkylene. As usedherein percent by weight or parts by weight refer to, or are based on,the weight or the compounds or compositions described unless otherwisespecified. Unless otherwise stated parts by weight are based 100 partsof the relevant composition.

First Component

The first component may be a homopolymer consisting substantially of oreven entirely of a 1,1-disubstiuted-1-alkene compound, or a copolymerincluding one or more 1,1-disubsituted-1-alkene compounds. The copolymermay include two or more different 1,1-disubstituted-1-alkene compounds.The copolymer may include a monomer that is not a1,1-disubstituted-1-alkene compound, but is capable of copolymerizingwith the 1,1-disubstituted-1-alkene compound. The copolymer may be arandom copolymer or a block copolymer. Some or all of the1,1-disubstituted-1-alkene compound is attached to the second component.The first component may include a cross-linker for cross-linking thecopolymer of the first component and/or for forming a network structure.

1,1-Disubstituted-1-Alkene Compound

The composition disclosed include 1,1-disubstituted-1-alkene compoundswhich preferably are 1,1-dicarbonyl substituted alkene compounds.Preferred 1,1-dicarbonyl substituted alkene compounds are 1,1-dicarbonylsubstituted ethylene compounds. 1,1-dicarbonyl substituted ethylenecompounds refer to compounds having a carbon with a double bond attachedthereto and which is further bonded to two carbonyl carbon atoms.Exemplary compounds are shown in Formula 1:

wherein R is a hydrocarbyl group which may contain one or moreheteroatoms and X is oxygen or a direct bond (such as a methyleneß-ketoester). Exemplary classes of 1,1-dicarbonyl substituted ethylenesare the methylene malonates, methylene beta-keto ester or diketones.Methylene malonates are exemplified by Formula 2:

R may be separately in each occurrence alkyl, alkenyl, C₃-C₉ cycloalkyl,heterocyclyl, alkyl heterocyclyl, aryl, aralkyl, alkaryl, heteroaryl, oralkheteroaryl, or polyoxyalkylene, or both of the R's form a 5-7membered cyclic or heterocyclic ring. R may be separately in eachoccurrence C₁-C₁₅ alkyl, C₂-C₁₅ alkenyl, C₃-C₉ cycloalkyl, C₂₋₂₀heterocyclyl, C₃-20 alkheterocyclyl, C₆₋₁₈ aryl, C₇₋₂₅ alkaryl, C₇₋₂₅aralkyl, C₅₋₁₈ heteroaryl or C₆₋₂₅ alkyl heteroaryl, or polyoxyalkylene,or both of the R groups form a 5-7 membered cyclic or heterocyclic ring.The recited groups may be substituted with one or more substituents,which do not interfere with the reactions disclosed herein. Preferredsubstituents include halo alkylthio, alkoxy, hydroxyl, nitro, azido,cyano, acyloxy, carboxy, or ester. R may be separately in eachoccurrence C₁-C₁₅ alkyl, C₃-C₆ cycloalkyl, C₄₋₁₈ heterocyclyl, C₄₋₁₈alkheterocyclyl, C₆₋₁₈ aryl, C₇₋₂₅ alkaryl, C₇₋₂₅ aralkyl, C₅₋₁₈heteroaryl or C₆₋₂₅ alkyl heteroaryl, or polyoxyalkylene. R may beseparately in each occurrence a C₁₋₄ alkyl. R may be separately in eachoccurrence methyl or ethyl. R may be the same for each ester group onthe 1,1-dicarbonyl substituted ethylenes. Exemplary compounds aredimethyl, diethyl, ethylmethyl, dipropyl, dibutyl, diphenyl, andethyl-ethyl gluconate malonates; or dimethyl and diethyl methylenemalonate (R is either methyl or ethyl).

The 1,1-dicarbonyl substituted ethylene compounds disclosed hereinexhibit a sufficiently high purity so that it can be polymerized. Thepurity of the 1,1-dicarbonyl substituted ethylenes may be sufficientlyhigh so that 70 mole percent or more, preferably 80 mole percent ormore, more preferably 90 mole percent or more, even more preferably 95mole percent or more, and most preferably 99 mole percent or more of the1,1-dicarbonyl substituted ethylenes is converted to polymer during apolymerization process. The purity of the 1,1-dicarbonyl substitutedethylenes is about 96 mole percent or greater, about 97 mole percent orgreater, about 98 mole percent or greater, about 99 mole percent orgreater, or about 99.5 mole percent or greater, based on the totalweight of the 1,1-dicarbonyl substituted ethylenes. The 1,1-dicarbonylsubstituted ethylenes contain 4 mole percent or less of 1,1-dicarbonylsubstituted-1,1 bis (hydroxymethyl)-methanes, 3 mole percent of less of1,1-dicarbonyl substituted-1,1 bis (hydroxymethyl)-methanes, 2 molepercent of less of 1,1-dicarbonyl substituted-1,1 bis(hydroxymethyl)-methanes, 1 mole percent of less of 1,1-dicarbonylsubstituted-1,1 bis (hydroxymethyl)-methanes, or 0.5 mole percent ofless of 1,1-dicarbonyl substituted-1,1 hydroxymethyl-methanes. Theconcentration of any impurities containing a dioxane group preferably isabout 2 mole percent or less, more preferably about 1 mole percent orless, even more preferably about 0.2 mole percent or less, and mostpreferably about 0.05 mole percent or less, based on the total weight ofthe 1,1-dicarbonyl substituted ethylenes. The total concentration of anyimpurity having the alkene group replaced by an analogous hydroxyalkylgroup (e.g., by a Michael addition of the alkene with water) preferablyis about 3 mole percent or less, more preferably about 1 mole percent orless, even more preferably about 0.1 mole percent or less, and mostpreferably about 0.01 mole percent or less, based on the total moles inthe 1,1-dicarbonyl substituted ethylenes. Preferred 1,1-dicarbonylsubstituted ethylenes are prepared by a process including one or more(e.g., two or more) steps of distilling a reaction product or anintermediate reaction product (e.g., a reaction product or intermediatereaction product of a source of formaldehyde and a malonic acid ester).

The functional compound may include one or more methylene malonateswhich may be the same or different.

The 1,1-disubstituted-1-alkene compound may include one or anycombinations of the 1,1-disubstitued alkene compounds and1,1-disubstituted ethylene compounds disclosed in U.S. Pat. No.9,249,265 B1, issued Feb. 2, 2016 (see e.g., column 5, line 44 throughcolumn 10, line 30), incorporated herein by reference in its entirety.

Particularly preferred monomers include methyl propyl methylenemalonate, dihexyl methylene malonate, di-isopropyl methylene malonate,butyl methyl methylene malonate, ethoxyethyl ethyl methylene malonate,methoxyethyl methyl methylene malonate, hexyl methyl methylene malonate,dipentyl methylene malonate, ethyl pentyl methylene malonate, methylpentyl methylene malonate, ethyl ethylmethoxy methylene malonate,ethoxyethyl methyl methylene malonate, butyl ethyl methylene malonate,dibutyl methylene malonate, diethyl methylene malonate (DEMM), diethoxyethyl methylene malonate, dimethyl methylene malonate, di-N-propylmethylene malonate, ethyl hexyl methylene malonate, methyl fenchylmethylene malonate, ethyl fenchyl methylene malonate, 2-phenylpropylethyl methylene malonate, 3-phenylpropyl ethyl methylene malonate, anddimethoxy ethyl methylene malonate.

The 1,1-disubstituted-1-alkene compound may be a compound prepared by atransesterification, such as described in U.S. Provisional PatentApplication No. 62/421,754, filed on Nov. 14, 2016, the contents ofwhich are incorporated herein by reference in its entirety.

Cross-Linker

The first component may include a cross-linker. The cross-linker may beemployed for cross-linking the polymer and/or for forming a networkstructure. The cross-linker may be a compound that copolymerizes withthe other monomers of the first component. For example, the cross-linkermay include one or more (preferably two or more) alkene groups.Preferably, each alkene group is capable of polymerizing on a separatepolymer molecules to form a link between the polymer molecules. Asanother example, the cross-linker may attach to a functional group(i.e., a functional group other than the alkene group) on each of twopolymer molecules to connect the two polymer molecules. The cross-linkermay be a multifunctional monomer, such as described herein.

Multifunctional Monomer

The 1,1-disubstituted-1-alkene compound may include a multi-functionalcompound including two or more alkene groups. Examples ofmulti-functional compounds that may be employed herein include thosedescribed in U.S. Pat. No. 9,249,265 B1, issued Feb. 2, 2016 (see e.g.,column 9, line 12 through column 9, line 46), incorporated herein byreference in its entirety. Other examples of multi-functional compoundshaving a plurality of alkenyl groups includes those described in USPatent Application Publication US 2016/0068616 A1 (see e.g., paragraph0042), incorporated herein by reference. For example, some or all of the1,1-disubstituted alkenes can also be multifunctional having more thanone core unit and thus more than one alkene group. Exemplarymultifunctional 1,1-disubstituted alkenes are illustrated by theformula:

wherein R¹, R² and X are as previously defined; n is an integer of 1 orgreater; and R is a hydrocarbyl group, and the 1,1-disubstituted alkenehas n+1 alkenes. Preferably n is 1 to about 7, and more preferably 1 toabout 3, and even more preferably 1. In exemplary embodiments R² is,separately in each occurrence, straight or branched chain alkyl,straight or branched chain alkenyl, straight or branched chain alkynyl,cycloalkyl, alkyl substituted cycloalkyl, aryl, aralkyl, or alkaryl,wherein the hydrocarbyl groups may contain one or more heteroatoms inthe backbone of the hydrocarbyl group and may be substituted with asubstituent that does not negatively impact the ultimate function of thecompounds or polymers prepared from the compounds. Exemplarysubstituents are those disclosed as useful with respect to R¹. Incertain embodiments R² is, separately in each occurrence, C₁₋₁₅ straightor branched chain alkyl, C₂₋₁₅ straight or branched chain alkenyl, C₅₋₁₈cycloalkyl, C₆₋₂₄ alkyl substituted cycloalkyl, C₄₋₁₈ aryl, C₄₋₂₀aralkyl or C₄₋₂₀ aralkyl groups. In certain embodiments R² is separatelyin each occurrence C₁₋₈ straight or branched chain alkyl, C₅₋₁₂cycloalkyl, C₆₋₁₂ alkyl substituted cycloalkyl, C₄₋₁₈ aryl, C₄₋₂₀aralkyl or C₄₋₂₀ alkaryl groups.

If employed, the amount of the multi-functional compound preferably issufficiently low so that the glass transition temperature of the polymeris not greatly affected by the network structure formed by thecross-links formed upon polymerization. For example, any increase in theglass transition temperature due to the multi-functional compoundpreferably is about 50° C. or less. Preferably the amount of themulti-functional compound is about 50 weight percent or less, morepreferably about 30 weight percent or less, and most preferably about 12weight percent or less, based on the total weight of the1,1-disubstituted-1-alkene compounds (e.g., in the polymerizablecomposition or in the grafted polymer). The amount of themulti-functional compound preferably is sufficiently high so that anetwork or other cross-linked structure is obtained and/or foraccelerating the polymerization reaction. A network structure may beparticularly useful in avoiding the grafted polymer from being entirelyabsorbed in water. Acceleration in the polymerization reaction may beparticularly useful for reducing setting time of an adhesive or coatingincluding the grafted polymer. The amount of the multi-function compoundpreferably is present in an amount of about 0.2 weight percent or more,more preferably about 0.5 weight percent or more, even more preferablyabout 1.5 weight percent or more, and most preferably about 3.6 weightpercent or more, based on the total weight of the1,1-disubstituted-1-alkene compounds.

Second Component

Some or all of the 1,1-disubstituted-1-alkene compound (e.g., the1,1-diester-1-alkene compound) is grafted with a second component thatimparts hydrophilic characteristics to the grafted compound. The secondcomponent (i.e., the hydrophilic component) may be a water-solublepolymer or a functional compound having ionic characteristics.

Hydrophilic component may include an oligomeric polymer (e.g., having amolecular weight from about 200 g/mole to about 8500 g/mole) or a highmolecular weight polymer (having a molecular weight greater than 8500g/mole). Such polymer include polyacrylamide homopolymers andcopolymers, polyvinyl alcohol hompolymers and copolymers, polyacrylicacid homopolymers and copolymers, polyalkoxide homopolymers andcopolymers (e.g., polyethylene oxide), amine containing polymers (e.g.,polyamines, polyethyleneimines, and polymers including quaternaryammonium compounds), copolymers of vinyl methyl ether and maleicanhydride, and polyvinylpyrrolidone homopolymers and copolymers.

The second component may include or consist essentially of one or morequaternary ammonium compounds, such as a salt having a cation with thefollowing structure:

where the nitrogen is bonded to four carbon atoms. Preferably, thenitrogen atom is directly attached to one or more alkoxy groups. Forexample, the quaternary ammonium compound may have the structure:

where X⁻ is a counter anion. Preferably, R¹, R², R³, and R⁴ are eachalkyl or alkoxy groups, and most preferably C₁, C₂, C₃, or C₄ alkyl orC₁, C₂, C₃, or C₄ alkoxy groups. The number of alkoxy groups on thequaternary ammonium compound may be one, two or more, and is mostpreferably one.

The counter anion for the quaternary ammonium compound may be any anion.Examples of anions include halogen anions (fluoride ion, chloride ion,bromide ion, or iodide ion), hydroxide ion, acetate ion, chlorate ion,sulfate ion, nitrate ion, perchlorate ion, and sulfite ion, nitrite ion,sulfate anions, sulfite anions, and carbonate ions. Particularlypreferred anions include sulfite ions, nitrate ions, and carbonate ions.

Grafting or Transesterification Reaction

The second component may be grafted onto the 1,1-disubstituted-1-alkenecompound (e.g., the 1,1-diester-1-alkene compound) using any methodcapable of connecting the compounds. Preferably the1,1-disubstituted-1-alkene compound is directly connected to the secondcomponent by a covalent bond. A preferred reaction for grafting thesecond component is a transesterification reaction. Thetransesterification reaction may employ one or more catalysts. It willbe appreciated that the grafting reaction may occur before or after thepolymerization of the 1,1-disubstituted-1-alkene compound. Preferablythe grafting reaction is performed prior to the polymerization reaction.

An illustrative grafting reaction is shown below, where a1,1-disubstituted-1-alkene compound (e.g., DEMM) is reacted with aquaternary ammonium salt by a transesterification reaction using acatalyst (e.g., an acid catalyst or an enzymatic catalyst).

Another illustrative grafting reaction is shown below, where a1,1-disubstituted-1-alkene compound (e.g., DEMM) is reacted with awater-soluble polymer (e.g., polyethylene glycvol) by atransesterification reaction.

Catalyst

The transesterification reactions according to the teachings herein aretypically performed in the presence of one or more catalysts. Thetransesterification catalyst may be an acid, an ester of such acid or anenzyme. The transesterification catalyst may be an enzyme. Thetransesterification catalyst may be a lipase enzyme. Atransesterification process utilizing an enzyme is disclosed in US2014/0329980, incorporated herein by reference for all purposes in itsentirety.

The transesterification catalyst may be one or more acids having a pKain a polar aprotic solvent of about −5 to about 14 or esters of theacids. The acid or the ester of the acid may be present in an amount ofabout 3.0 molar equivalents or less of the acid or the ester of acid permolar equivalent of the ester containing compounds transesterified. Whenthe catalyst is an acid or an ester of an acid the method may beperformed at a temperature of about 20° C. to about 160° C. Thetransesterification catalyst may be a lipase enzyme catalyst. When thecatalyst is a lipase enzyme catalyst the transesterification step isperformed at an elevated temperature between about 20° C. and 70° C.During the transesterification reaction, volatile by-products may beformed and removed from the reaction mixture. The volatile by-productsmay be removed from the reaction mixture by applying a vacuum. Thevolatile by-products may be alcohols.

The catalyst may be an acid or an ester thereof. The transesterificationprocess using an acid or ester is disclosed in U.S. patent applicationSer. No. 14/814,961 filed Jul. 31, 2015, incorporated herein byreference for all purposes in its entirety. Any acid or ester thereofthat catalyzes transesterification while minimizing side reactions maybe used. In some embodiments the acid or acid utilized to form an esteris an acid having a pKa in a polar aprotic solvent, such as acetonitrileor dioxane, as disclosed hereinafter. In particular the pKa is chosen toefficiently catalyze the transesterification reaction while minimizingside reaction and the concentration of catalyst in a reaction mixture.The acid used may have a pKa of about −5 or greater, about −3 orgreater, or about 1.0 or greater. The acid used may have a pKa of about14 or less, about 11 or less, or about 9 or less. The acid can be aBronsted acid having a pKa as disclosed. The catalyst may be a superacidor an ester thereof. Superacid means an acid having an acidic strengthgreater than the strength of 100 percent sulfuric acid. Ester thereof,in the context of the acid catalysts, refer to compounds wherein thehydrogen on the acid is replaced with a hydrocarbyl group, preferably analkyl group. Superacids are acids having a strength greater than thestrength of 100 percent sulfuric acid, a pKa less than 100 percentsulfuric acid, that is less than 8, more preferably less than about 5,and most preferably less than about 2. The measurement of acid strengthis based on Kutt et al. “Equilibrium Acidities of Super Acids,” Journalof Organic Chemistry Vol 76 pages 391 to 395, 2011, published on the WebDec. 17, 2010, which is incorporated herein by reference. Exemplarysuper acids include trifluoromethanesulfonic acid (triflic acid),sulfated tin oxide, triflated tin oxide, sulfated zirconia, triflatedzirconia, and triflated HZSM-5. The most preferred super acids aretriflic acid and fluorosulfonic acid.

Exemplary acid catalysts include triflic acid, fluorosulfonic acid, andsulfuric acid. For reactions requiring monosubstitution (only onehydroxyl group on the alcohol is being replaced by transesterification),weaker acids with pKa values equal to or higher than sulfuric acid maybe desired. Examples of such acids include sulfuric acid ormethanesulfonic acid. For reactions requiring disubstitution (twohydroxyl groups on the alcohol are being replaced bytransesterification), stronger acids with pKa values equal to or lowerthan sulfuric acid may be desired. Examples of such acids includesulfuric acid, fluorosulfonic acid, and triflic acid. For reactionsrequiring polysubstitution (more than 2 hydroxyl groups on the alcohol),choice of acid catalysts can be similar to that for disubstitutionreactions but reaction time may need to be increased. Esters of acidsuseful as catalysts include alkyl triflates.

The catalyst can be mixed with the reactants or can be supported on asubstrate such as a membrane or an inert carrier such as a poroussupport structure (the catalysts can be heterogeneous). Catalysts whichare not supported are commonly referred to as homogeneous. The catalystcan be used in any concentration that catalyzes the transesterificationreaction. The amount of catalyst utilized for the reaction depends onthe type of catalyst being chosen. The concentration of catalyst isabout 3 molar equivalents or less per equivalent of the ester compoundsundergoing transesterification; about 1 molar equivalents or less; about0.5 molar equivalents or less; about 0.1 molar equivalents or less. Theconcentration of catalyst is about 0.01 molar equivalents or greater perequivalent of the ester compounds undergoing transesterification; andmost preferably about 0.1 molar equivalents or greater. Higherconcentrations of catalysts than recited may be utilized. As disclosedin Malofsky et al., U.S. Pat. Nos. 8,609,885 and 8,884,051; and Malofskyet al. WO 2013/059473 the presence of acid in the 1,1-disubstitutedalkene compounds recovered can present problems with respect to use ofthe compounds and low concentrations of acid in the products in use isdesired. If high levels of acid are contained in the final product,additional purification or removal steps may be required. The amountsrecited achieve the balance between efficient catalysis and the need forlow acid concentrations in the product for use. In embodiments when thecatalyst is selected from sulfuric acid or those acids having pKa valuesless than that of sulfuric acid, the concentration of such catalysts inthe reaction mixture is preferably at the upper end of the rangesrecited herein.

The catalyst may include or consist entirely of an enzymatic catalyst.Any enzymatic catalyst suitable for catalyzing the transesterificationreaction may be used. Various enzymatic catalysts are described in U.S.Pat. No. 7,972,822 B2 (by Gross et al., issued on Jul. 5, 2011, see forexample column 8, lines 2-4 and 7-35), U.S. Pat. No. 5,416,927 A (byZaks et al., issued May 31, 1994, see for example column 2, line 64 tocolumn 3, line 12), U.S. Pat. No. 5,288,619 A (by Brown et al., issuedFeb. 22, 1994, see for example column 4, line 18 to column 5, line 17),US Patent Application Publication 2016/177,349 A1 (by Addy et al.,published Jun. 23, 2016, see for example paragraphs 0046-0048), U.S.Patent Application Publication 2014/0017741 A1 (by Nielsen et al.,published Jan. 16, 2014, see for example paragraphs 0026-0029); thecontents of which are each incorporated herein by reference.

Many different enzymes may be employed in enzymatic catalytictransesterification reactions for wax esters, including those that arederived/obtained from biological organisms, those made synthetically,and those that are entirely artificial, whether made biologically and/orsynthetically. For those enzymes that are lipases, these may include,one, some, any, or any combination of lipases derived from the followingorganisms: Aspergiilus niger, Aspergillus oryzae, Bacillus subtilis,Bacillus thermocatenulatus, Burkholderia cepacia, Burkhoideria glumae,Candida rugosa, Candida antarctica A, Candida antarctica B. rugosa,Candnda antarctica A, Candida antarctica B, Candida cylindracea, Candidaparapsilosis, Chromobacterium viscosum, Geotrichum candidum, Geotrichumsp., Mucor miehei, Humicola lanuginose, Penicillium camemberti,Penicillium chrysogenum, Penicillium roqueforti, Pseudomonas cepacia,Pseudomonas aeruginosa, Pseudomonas fluorenscens, Pseudomonas fragi,Pseudomonas alcaligenes, Pseudomonas mendocina, Rhizopus arrhizus,Rhizomucor miehe, Staphylococcus hyicus, Staphylococcus aereus,Staphylococcus epidermidis, Staphylococcus warneria, Staphylococcusxylosus, Thermormyces lanuginosus, Aspergillus sp., Bacillus sp.,Burkholderia sp., Candida sp., Chromobacterium sp., Geotrichum sp, Mucorsp, Humicola sp, Penicillium sp, Pseudoronas sp, Rhizopus sp.,Staphylococcus sp, and Thermomyces sp. The lipase may include or consistessentially of one or any combination of the following: a lipase fromThermomyces lanuginosus marketed under the tradenames LIPOZYME TL IM orLIPEX by Novozymes A/S of Bagsvaerd, Denmark and immobilized on asubstrate also manufactured by Novozymes; the lipase may be thatmarketed under the tradename NOVOZYM by Novozymes, A/S derived fromCandida antarctica; those marketed under the tradenames CALB L, NOVOZYME435, NOVOCOR AD L, AND LIPOLASE 100 L by Novozymes; those marketed underthe tradenames CALB, CALA, and GRL by c-LEcta, GMBH of Leipzig, Germany;those marketed under the tradenames LIPASE A “AMANO” 12, LIPASE AY“AMANO” 30SD, LIPASE G “AMANO” 50, LIPASE R “AMANO”, LIPASE DF “AMANO”15, LIPASE MER “AMANO”, and NEWLASE F by Amano Enzyme Inc. of Nagoya,Japan; those marketed under the tradenames LIPASE MY, LIPASE OF, LIPASEPL, LIPASE PLC/PLG, LIPASE QLM, LIPASE QLC/OQLG, LIPASE SL, and LIPASETL by Meito Sangyo Co., Ltd., of Nagoya, Japan, a lipase from Candidaantarctica A, a lipase from Candida antarctica B, and a lipase fromCandida rugosa. In various implementations, the lipases preferably haveat least 60%, at least 70%, at least 80%, at least 90%, at least 95%, atleast 96%, at least 97%, at least 98%, or even at least 99% identity toany of the lipases disclosed herein, and in the patent applicationsdisclosed herein, all of which have been previously incorporated byreference.

Polymerization of the Grafted 1,1-Disubstituted-1-Alkene

The grafted 1,1-disubstituted-1-alkene compound may be polymerized byreacting the alkene group onto a growing polymer chain. Preferably about70% or more, even more preferably about 90% or more, and most preferablyabout 98% or more of the alkene groups are polymerized. Preferably, thepolymer includes a sufficient amount of the hydrophilic component (e.g.the water-soluble polymer and/or the cation containing compound) so thatthe resulting grafted polymer is hydrophilic or water-soluble. Thepolymerization reaction may be catalyzed (e.g., usingtetramethylguanidine).

The polymerization of a grafted 1,1-disubstituted alkene including awater-soluble polymer is illustrated below.

The polymerization of a grafted 1,1-disubstituted alkene including acation containing compound is illustrated below.

The polymerization reaction may occur at one or more reactiontemperatures sufficiently high for converting the monomer into polymer.As the polymerization reaction progresses, the polymerizable compositionmay become a viscous liquid, a glassy liquid (e.g., below the glasstransition temperature of the polymer) or even a solid (e.g., below themelting temperature of the polymer). Preferably, the reactiontemperature is above the glass transition temperature of the resultingpolymer (e.g., of the first component). Preferably, the reactiontemperature is above any melting temperature of the resulting polymer.As an alternative, the process may include an initial polymerization ata relatively low temperature (e.g., below any melting temperature and/orbelow the glass transition temperature of the polymer) and then theprocess may include a secondary polymerization reaction at a highertemperature (e.g., above the melting temperature and/or above the glasstransition temperature of the polymer). The reaction temperature andreaction time may be selected to provide a desired level ofpolymerization and/or a desired level of cross-linking.

Polymerizable System (i.e., Polymerizable Composition)

One aspect according to the teachings herein, is directed at apolymerizable system including the grafted 1,1-disubstituted alkenecompound (e.g., grafted with the quaternary ammonium compound or with awater-soluble polymer) and preferably further including one or more1,1-disubstituted alkene compounds (e.g., a methylene malonate monomer)that is free of any such graft. The methylene malonate monomer may beselected so that it will copolymerize with the alkenyl groups of thegrafted compound. It will be appreciated that the grafted compound mayinclude a 1,1-disubstituted-1-alkene compound that is the same ordifferent from the methylene malonate monomer.

Any of the methylene malonate compounds described herein with respect tothe graft compound having an alkenyl group for the may be employed as anadditional monomer in the polymerizable composition. It will beappreciated that methylene malonate monomer may be replaced in part orin whole with dimers, trimers, or longer oligomers (e.g., having adegree of polymerization of about 4 to 50, about 4 to 15, or about 4 to8).

The polymerizable system may include a sufficient amount of a stabilizerto prevent or minimize polymerization of the polymerizable system. Theprocess may include a step of activating the polymerizable system forpolymerizing the methylene malonate monomers and alkenyl group(s)attached to the grafted compound.

It will be appreciated that the polymerizable system may be used to forma grafted polymer that is a block copolymer including a first blockincluding one or more 1,1-disubstituted alkene compounds and a secondblock including the water-soluble polymer. The amount of the firstpolymer block preferably is about 10 weight percent or more, morepreferably about 20 weight percent or more, even more preferably about25 weight percent or more, and most preferably about 30 weight percentor more, based on the total weight of the block copolymer. The amount ofthe first block may be about 90 weight percent or less, about 80 weightpercent or less, about 70 weight percent or less, about 60 weightpercent or less, or about 50 weight percent or less, based on the totalweight of the block copolymer.

The amount of the water-soluble polymer in the block copolymerpreferably is about 10 weight percent or more, more preferably about 20weight percent or more, even more preferably about 30 weight percent ormore, even more preferably about 40 weight percent or more, and and mostpreferably about 50 weight percent or more, based on the total weight ofthe block copolymer. The amount of the water-soluble polymer may beabout 90 weight percent or less, about 80 weight percent or less, about75 weight percent or less, or about 70 weight percent or less, based onthe total weight of the block copolymer. The ratio of the weight of thefirst component to the weight of the water-soluble polymer in the blockcopolymer may be about 0.05 or more, about 0.10 or more about 0.20 ormore or about 0.45 or more, or about 0.60 or more. The ratio of theweight of the first component to the weight of the water-soluble polymermay be about 10 or less, about 8 or less, about 6 or less, about 4 orless, about 3 or less, or about 2 or less.

The grafted 1,1-disubstituted alkene compounds and/or polymerizablesystem may be used for a film or coating. The film or coatings may havea thickness of about 0.001 μm or more, about 0.1 μm or more, about 1 μmor more, or about 2 μm or more. The coating or film preferably has athickness of about 200 μm or less, more preferably about 50 μm or less,and most preferably about 20 μm or less.

The grafted polymer may be used in a polymeric composition includingabout 10 weight percent or more of the grafted polymer and about 0.5 toabout 90 weight percent of one or more compounds selected from the groupconsisting of a filler, a stabilizer, a process aid, a biocide, apolymer, a colorant, a salt, and any combination thereof. For example,the polymeric composition may include a sufficient amount of a salt sothe polymeric composition is an electrical conductor.

The second component may impart useful characteristics to the1,1-disubstituted alkene compound (or the resulting grafted polymer) foruse in oil field applications. For example, the grafted compound may beused as an oil-wetting agent, a bactericide, or a corrosion inhibitor.

The compositions, compounds and grafted polymers according to theteachings herein may be employed in various applications that takeadvantage of feature of one or both of the components of the graftedpolymer. In particular, these materials may be employed in electronics(conducting polymers), as a surfactant, an ionomer, in a pharmaceuticalprocess, in petroleum recovery in water treatment, as a flocculant, in ahydrometallurgy process, or as a detergent. Other applications includeas a hydrophilic coating. For example, such a coating may be useful foranti-fouling applications. Without being bound by theory, it is believedthat the high amount of hydration may provide a surface difficult forproteins and microorganisms to attach to. As such, the materialsaccording to the teachings herein may prevent or reduce the accumulationof bio-organisms on a surface. These may be used for protecting againstfouling by plants, algae, microorganisms, or animals. The material andcompositions according to the teachings herein may be particularly usedon surfaces that are at least partially submerged in a body of watercontaining organisms capable of fouling or otherwise attaching to thesurface. They may be used for preventing fouling by calcerous foulingorganisms include mussels (e.g., zebra mussels), mollusks, barnacles,and other organisms that form a hard calcium carbonate containingstructure. They may be used for preventing fouling by non-calcerousorganisms include algae, biofilm, seaweed and other organisms that lacka calcium carbonate containing structure. The materials and compositionsaccording to the teachings herein may be used for removing water fromsurfaces and/or for keeping surfaces dry. The materials and compositionsaccording to the teachings herein may be used for converting liquidwaste to a stable solid or other structure where the liquid is absorbedby the grafted polymer. This may be particularly useful where the liquidincludes chemically hazardous compounds, biologically hazardousmaterials, toxic materials, or environmentally hazardous substances.

Any numerical values recited herein include all values from the lowervalue to the upper value in increments of one unit provided that thereis a separation of at least 2 units between any lower value and anyhigher value. As an example, if it is stated that the amount of acomponent or a value of a process variable such as, for example,temperature, pressure, time and the like is, for example, from 1 to 90,preferably from 20 to 80, more preferably from 30 to 70, it is intendedthat values such as 15 to 85, 22 to 68, 43 to 51, 30 to 32 etc. areexpressly enumerated in this specification. For values which are lessthan one, one unit is considered to be 0.0001, 0.001, 0.01 or 0.1 asappropriate. These are only examples of what is specifically intendedand all possible combinations of numerical values between the lowestvalue and the highest value enumerated are to be considered to beexpressly stated in this application in a similar manner. As can beseen, the teaching of amounts expressed as “parts by weight” herein alsocontemplates the same ranges expressed in terms of percent by weight.Thus, an expression in the Detailed Description of the Invention of arange in terms of at “‘x’ parts by weight of the resulting polymericblend composition” also contemplates a teaching of ranges of samerecited amount of “x” in percent by weight of the resulting polymericblend composition.”

Unless otherwise stated, all ranges include both endpoints and allnumbers between the endpoints. The use of “about” or “approximately” inconnection with a range applies to both ends of the range. Thus, “about20 to 30” is intended to cover “about 20 to about 30”, inclusive of atleast the specified endpoints.

The disclosures of all articles and references, including patentapplications and publications, are incorporated by reference for allpurposes. The term “consisting essentially of” to describe a combinationshall include the elements, ingredients, components or steps identified,and such other elements ingredients, components or steps that do notmaterially affect the basic and novel characteristics of thecombination. The use of the terms “comprising” or “including” todescribe combinations of elements, ingredients, components or stepsherein also contemplates embodiments that consist essentially of theelements, ingredients, components or steps.

Plural elements, ingredients, components or steps can be provided by asingle integrated element, ingredient, component or step. Alternatively,a single integrated element, ingredient, component or step might bedivided into separate plural elements, ingredients, components or steps.The disclosure of “a” or “one” to describe an element, ingredient,component or step is not intended to foreclose additional elements,ingredients, components or steps.

It is understood that the above description is intended to beillustrative and not restrictive. Many embodiments as well as manyapplications besides the examples provided will be apparent to those ofskill in the art upon reading the above description. The scope of theinvention should, therefore, be determined not with reference to theabove description, but should instead be determined with reference tothe appended claims, along with the full scope of equivalents to whichsuch claims are entitled. The disclosures of all articles andreferences, including patent applications and publications, areincorporated by reference for all purposes. The omission in thefollowing claims of any aspect of subject matter that is disclosedherein is not a disclaimer of such subject matter, nor should it beregarded that the inventors did not consider such subject matter to bepart of the disclosed inventive subject matter.

EXAMPLES Example 1

Example 1 is a reaction mixture including a methylene malonate monomergrafted with a polyalkylene glycol and unreacted methylene malonatemonomer. The grafting reaction is carried out using PEGylation process.

CARBOWAX™ PEG 300 polyethylene glycol (commercially available from DOWCHEMICAL COMPANY) is purified by passing through an alumina column toresidual base catalyst. The polyethylene glycol has a number averagemolecular weight of about 285 to 300 g/mole, a hydroxyl number of about340 to 394 mg KOH/g, a melting range of about −15° C. to about −8° C.,and a heat of fusion of about 37 cal/g. A 250 mL round bottom flask ischarged with about 30 g (0.17 mol) of DEMM, about 3 g (10 wt % of theDEMM) of CLEA 102B4 enzyme and about 16.6 g (0.083 mol) of the PEG 300(alumina passed). The flask is connected to a rotary evaporator with avacuum of about 200 mm Hg and heated to about 45° C. for 2 hrs. Thevacuum removes ethanol as a reaction by-product. The enzyme is thenfiltered from the reaction mixture using a cotton plug in 20 ml syringe.NMR results indicate that about 35 percent of the DEMM is reacted to thePEG and about 65 percent of the DEMM remains as unreacted monomer in thereaction mixture. FIG. 1 shows the NMR for the reaction mixture.

The grafted DEMM may have a structure including a central polymerportion including a polyalkoxide and terminal methylene malonate groupshaving one or more (or all) of the features illustrated below:

The reaction mixture of the grafted DEMM is drawn down on apre-initiated (0.1% Na-benzoate in butyl cellosolve) cold rolled steelpanel using a Meyer Rod 10 resulting in a 25-micron thick coating afterfull cure at room temperature for 24 hours followed by heating at 82° C.for 1 hour. The coating displays hydrophilic character with waterwetting the surface with ease and eventually permeating through thecoating layer on continued exposure. A similar coating drawn down withonly DEMM monomer demonstrates no hydrophilic character. Thisdemonstrates the hydrophilicity imparted by polyethylene glycol in DEMMbased coatings.

Example 2

Example 2 is a reaction mixture including a polyalkylene glycol graftedonto a methylene malonate monomer and unreacted methylene malonatemonomer. The grafting of the polyalkylene glycol is carried out using anacid catalyzed transesterification process.

A three neck (250 mL) round bottom flask with a distillation head,thermometer, vacuum adapter, and a collection flask are assembled usinghigh vacuum grade grease along with a heating mantle (and thermocouple)and a magnetic stir bar. To this round bottom flask set-up, a mixture ofabout 20 g (about 0.12 mol) of DEMM, about 4.6 g (about 0.023 mol) ofCARBOWAX™ PEG 200 polyethylene glycol (commercially available from DOWCHEMICAL COMPANY), about 0.02 g (about 1000 ppm) of MeHQ and about 0.3ml (about 0.0058 mol) of H₂SO₄ is charged. CARBOWAX™ PEG 200polyethylene glycol has a weight average molecular weight of about 190to 210 g/mole, an average hydroxyl number of about 535 to about 590 mgKOH/g, and a melting point below about −65° C. A reduced pressure ofabout 400 mm Hg is maintained during the reaction using a vacuum pump.The reaction mixture is then heated to about 130° C. and stirred forabout 2 hours. Ethanol is collected as a reaction byproduct. The amountof grafting of the PEG onto the DEMM is calculated using NMR. About 45percent of the DEMM is reacted with the PEG and about 55 percent of theDEMM remains as monomer.

The grafted compound may have a structure including a central polymerportion including a polyalkoxide and terminal methylene malonate groupshaving one or more (or all) of the features illustrated below:

Example 3

Example 3 is a reaction mixture including a glycerol ethoxylate graftedonto a methylene malonate monomer and unreacted methylene malonatemonomer. The grafting of the glycerol ethoxylate may be carried outusing a transesterification process.

A 250 mL round bottom flask is charged with about 30 g (about 0.17 mol)of DEMM, about 3 g (about 10 parts per 100 parts of DEMM) of enzymeNOVOZYME 435 candida antartica isoform B (commercially available fromNOVOZYME) and about 56 g (about 0.056 mol) of glycerol ethoxylate(having a number average molecular weight of about 1000, obtained fromSigma Aldrich). The flask is connected to a rotary evaporator withreduced pressure of about 200 mm Hg and is heated to about 55° C. forabout 8 hours. Ethanol is removed as a reaction byproduct. The enzyme isthen filtered from the product using cotton plug in a 20 ml syringe, forisolating the reaction mixture. NMR results are obtained of the reactionmixture and used to calculate the conversion of the glycerol ethoxylateto the end-capped product. About 40% of desired transesterified products(i.e., end-capped product) is observed. The NMR spectrum for thereaction mixture is shown in FIG. 2. It is believed that the reactionmixture includes disubstituted and trisubstituted glycerol ethoxylatereaction products. The resulting reaction mixture includes the graftedcompound having one or more of the features as shown in the structuresbelow.

The reaction mixture is drawn down on a pre-initiated (0.1% Na-benzoatein butyl cellosolve) cold rolled steel panel using a Meyer Rod 10resulting in a about 25-micron thick coating after full cure at roomtemperature for about 24 hours followed by heating at about 82° C. forabout 1 hour. The coating displays hydrophilic character with waterwetting the surface with ease and eventually permeating through thecoating layer on continued exposure. In comparison, a specimen preparedwith the reaction mixture replaced with only DEMM and cured under thesame conditions (e.g., resulting in a DEMM homopolymer) demonstrates nohydrophilic character. Thus, the DEMM grafted with glycerol ethoxylatemay be used to impart hydrophilicity in a coating (e.g., in a methylenemalonate coating, such as a DEMM based coatings).

Characterization of the Graft Polymer

The graft polymer may be evaluated for water solubility/hydrophilicitycharacteristics.

A primer solution of either about 0.1 wt % sodium benzoate or about 0.5wt % tetramethylguanidine (i.e, TMG) in ethanol is drawn down onto asteel panel using a meyer rod. The solvent is allowed to flash off atroom temperature. Then, 2 ml of a polymerizable composition (e.g.,including the second component directly attached to a methylene malonatecompound) is applied to the top of the panel and drawn down in a similarmanner using a meyer rod. The coating is left to cure at roomtemperature overnight for about 18 hours.

The cured coating is tested by applying a single drop of reverse osmosis(i.e., RO) water to the surface and measuring the amount of time for thecoating to be dissolved or the drop to be absorbed. The coating displayshydrophilic character with water wetting the surface of the coating withease and eventually permeating through the coating layer and preferablyremoving the coating on continued exposure.

Several graft polymers are prepared by mixing a dimethyl methylenemalonate monomer, diethyl methylene malonate functionalized withglycerol ethoxylate, and a cross-linker as shown in the table below andcoatings were tested in the following manner. The polymerization is onthe steel substrate treated with the primer solution as described above.

Composition FM1 FM2 FM3 FM4 FM5 DEMM functionalized glycerol 80 70 60 5030 ethoxylate, weight % Cross-linker, weight percent 10 20 10 20 35 D3M,weight percent 10 10 30 30 35

After polymerizing the first component, the first component includes arandom copolymer of the D3M, DEMM, and the cross-linker, where thecross-linker is a multi-functional 1,1-disubstituted-1-alkene compoundhaving a plurality of polymerizable alkene groups. The second component(i.e, the hydrophilic component) consists essentially of the glycerolethoxylate.

After curing overnight at room temperature, the time for the drop ofwater to solubilize the coating is measured. As the amount ofcross-linker is increased, the time for solubilizing the coating isincreased.

Samples are also prepared, as described above, except the coating isexposed to a secondary cure by heating for about 30 minutes at atemperature of about 80° C. After the secondary cure, the time forsolubilizing the coating is increased.

1-12. (canceled)
 13. A polymeric composition comprising: i) about 10weight percent or more of a grafted polymer comprising a first componentincluding a polymer formed by polymerizing one or more monomersincluding a 1,1-disubstituted-1-alkene compound attached to a secondcomponent that is a hydrophilic component, wherein the hydrophiliccomponent includes a cation or a water-soluble polymer, based on thetotal weight of the polymeric composition; and ii) about 0.5 to about 90weight percent of one or more compounds selected from the groupconsisting of a filler, a stabilizer, a process aid, a biocide, apolymer, a colorant, a salt, and any combination thereof.
 14. Apolymerizable composition comprising a 1,1-disubstituted-1-alkenecompound grafted to a water-soluble polymer.
 15. The polymerizablecomposition of claim 14, wherein i) the water-soluble polymer is graftedto two or more 1,1-disubstituted-1-alkene compounds; and/or ii) the1,1-disubstituted-1-alkene compound is grafted to a single water-solublepolymer.
 16. The polymeric composition of claim 13, wherein thehydrophylic component is the cation.
 17. The polymeric composition ofclaim 16, wherein the polymerizable composition is further characterizedby one or any combination of the following: i) the polymeric compositionincludes one or more 1,1-disubstituted-1-alkene compounds that are notattached to the cation or water-soluble polymer and free of anyunreacted water soluble polymers or cation; or ii) the polymericcomposition includes a cross-linker for cross-linking the1,1-disubstituted-1-alkene compounds; or the polymeric compositionincludes a catalyst for accelerating a polymerization reaction of the1,1-disubstituted-1-alkene compound.
 18. A method of forming a graftedcompound comprising a step of grafting a 1,1-diester-1-alkene compoundwith a quaternary ammonium compound or with a water-soluble polymer. 19.The method of claim 18, wherein the method includes one or anycombination of the following: i) the grafting step includes atransesterification reaction; ii) the water-soluble polymer is selectedfrom the group consisting of a polyacrylamide, a polyvinyl alcohol, apolyacrylic acid, a polyalkoxide, an water soluble amine containingpolymer, a copolymer of vinyl methyl ether and maleic anhydride,polyvinylpyrrolidone, a copolymer thereof, or any combination thereof;iii) the method includes a step of polymerizing the 1,1-diester-1-alkenecompounds.
 20. A method of forming a grafted polymer including a step ofpolymerizing the polymerizable composition of claim
 14. 21. A conductivepolymeric composition comprising: the grafted polymer of claim 20 dopedwith one or more salts.
 22. A coating comprising the composition ofclaim
 13. 23. A-A composition comprised of the grafted polymer of claim20 of wherein the polymeric composition is a surfactant, an ionomer, anantifouling agent, a composition for petroleum recovery, a compositionfor water treatment, a flocculant, a composition for hydrometallurgy, adetergent, a composition for a pharmaceutical process, or anycombination thereof.
 24. The polymerizable composition of claim 14,wherein the 1,1-disubstituted-1-alkene compound is grafted to twocations.
 25. The polymeric composition of claim 13, wherein the graftedpolymer has a network structure.
 26. The polymeric composition of claim13, wherein the first component includes a multifunctional1,1-disubstituted-1-alkene monomer having two or more polymerizablealkene groups.
 27. The polymeric composition of claim 13, wherein the1,1-disubstituted-1-alkene compound includes one or more1,1-diester-1-alkenes, having a structure:

wherein R is a hydrocarbyl group which may contain one or moreheteroatoms and X is oxygen or a direct bond.
 28. The polymericcomposition of claim 13, wherein the 1,1-disubstituted-1-alkene compoundis a methylene malonate having a structure:

wherein R is separately in each occurrence alkyl, alkenyl, C₃₋₉cycloalkyl, heterocyclyl, alkyl heterocyclyl, aryl, aralkyl, alkaryl,heteroaryl, or alkheteroaryl, or polyoxyalkylene, or both of the R'sform a 5-7 membered cyclic or heterocyclic ring.
 29. The method of claim18, wherein the grafting is catalyzed by an acid catalyst or anenzymatic catalyst.
 30. The method of claim 29, wherein the grafting iscatalyzed by a Bronsted acid.
 31. The polymerizable composition of claim14, wherein the 1,1-disubstituted-1-alkene compound includes one or more1,1-diester-1-alkenes, having a structure:

wherein R is a hydrocarbyl group which may contain one or moreheteroatoms and X is oxygen or a direct bond.
 32. The polymerizablecomposition of claim 14, wherein the 1,1-disubstituted-1-alkene compoundis a methylene malonate having a structure:

wherein R is separately in each occurrence alkyl, alkenyl, C₃₋₉cycloalkyl, heterocyclyl, alkyl heterocyclyl, aryl, aralkyl, alkaryl,heteroaryl, or alkheteroaryl, or polyoxyalkylene, or both of the R'sform a 5-7 membered cyclic or heterocyclic ring.